Azo dyes



Patented Oct. 9 1945 UNITED? STATE PATENT, OFFICE AZO DYES Moses LkCrossley and Byron L. West, Plainfield, N. J., assignors to American CyanamidCompany, New York, N. Y., a. corporation of Maine No Drawing.

4 Claims.

This invention relates to new azo'dyes containing hexylresorcinol as a component. 1

It has been proposed in the past to make certain azo dyes, particularly metallized azo dyes having resorcinol or dihydroxy naphthalene azo components. According to the present invention a newseries of azo dyes is obtained by using hexylresorcinol, 1,3 dihydroxy-4-hexyl-benzene in which R. is an aryl radical or an arylazo aryl radical and n is 1 or 2. When n is 1 and R is free from azo groups, monoazo dyes are obtained and when n is 2 dis or higher polyazo dyes result.

When one or moreof the aryl groups contain a metallizable group ortho to the azo group, the resulting dyes may be metallized withthe usual metals and give colors of excellent fastness.

The dyes of the present invention'may' be used for dyeing various materials such as animal or vegetable fibers. The dyes preferably should contain a solubilizing'group in one or more of the aryl radicals such as for example a sul'fonic group. When such solubilizing groups are absent water insoluble dyes are obtained which can be used for coloring organic solvents, plastics andthe like, as they are in general soluble in alcohols and aromatio hydrocarbons.

The dyes of the present invention maybe prepared by the usual methods. Thus, for example, when a monoazo dye is desired an aromatic amine is diazotized and coupled with the hexylresorcinol. Disazo dyes may be obtained by coupling. two molecularproportions of a diazotized arylamine with I the hexylresorcinol or if the amine'does .not containgroups capable ofazoic coupling the disazo dyes may be produced in two steps by first coupling one molecular proportion. of diazotized amine with hexylresorcinol and then coupling a' Application November 5, 1941, Serial No. 417,878

second portion of the same or a different diazotized aromatic amine with themonoazodye obtained. Another method of preparing di'sazodyes is to couple diazotized amino azo compoundswith hexylresorcinol." This method also permits producing polyazo dyes having more than two azo r ps The invention will be described in connection with the following specific examples which are illustrative. The parts are by weight. I Q

Example 1 r 154 parts of p-nitroaminophenol were dissolved in 200 parts of water and diazotized with theaddi; tion of 30 parts of. 36% hydrochloric acidand 69 parts of sodium nitrite at 10 C. 'and'cooled to 160 parts offsoda ash wereadded to the-dye produced by coupling 27.? parts of diazotized amino azo benzene p-sulfomc acid to 194 parts of hexylresorcinol. The nitroaminophenolw diazo was added to this dye and coupling allowed to stir overnight. The dye was precipitated by addition of 15 partsof sodium chloride per parts of volume and the'dye was filtered and dried.

Example 2 The diazo equivalent to 27.7 .parts" aminoazo benzene p-sulfonic acid; dissolved in 500 cc. of solution was coupled to 19.4 parts of hexylre sorcinol at 0 to 5 C. in the presence of 20% sodium acetate solution; 22.1 parts of sodium picramate were dissolved in 400 cc. of hot water and 30 parts of 36% hydrochloric acid were added and the and when dry it was a brown color'yihich dyed wool a brown .tone.

Examples of further dyes falling under the present invention are shown in the following table.-

First component Second component Third component Color OH OH H:N Brown.

1 aHla N=N OH H038 S 03H OH OH NH: D0. OzN NH; 0 OH:

N O a C 01113 N =N 803E OH NH: OH N H: D0.

N=N 0H 5033 OH NO NO: H &8

C s aa N=N NH CaHs OH NHz OH OH NH: Dark brown. N=N OH OH HOaS Ha S OaH aHxa N= OH NH: D0.

-OH -OH OH 01 V S 03H S 0311 Cu n NH: NH: OH NH: D0.

OH CH:

SOaH 05H N= 00113 S 0 H OH OH NH; Brown. H 038 NH 0111: NO, OH OH NH: D0. OzN NH: 0H

N O; OaHn First component" Third component I Second component 0H i Brawn.

. i I P- OzN NH:

on I

Hm-OONm-Oo- 5 1i 18 J W 7 V. Orapge.

First component Second component Third component Fourth component Color 31 N31 0H 7. Reddish l orange. OCH:

Ho 32 NHn 7 OH I Red.

uHn 33 OH HO Bronze.

HEN

on mots NH: Hm No, r on e u I 0111:

34 OH NH: OH Bordeaux.

NH.OO.GOONa 2 OH HaC CH3 CH3 OH lHlS HiN HzN 0 1s 35 7 NH: OH Brown. 0H 7 l (3) NaOOC DB 0,111. nlN NH: (2 SOaNa a Fifth component 36 HQN Do.

' 0H 0H NH:

v OH OH SOzNa 0H1: Ha NH! CuHi: SOaNa We claim: I 3... Disazc" dyes having the following formula: I 1. An azo dye containing hexylresorcinolco s 70H 'having' the following formula: g l

R1N=N N=NR;

0111: I o in which R1 and R2 are aryl radicals. v r 0 1: 4. Polyazo dyes having the following formula in which R is one or more radicals included in the 6 OH group consisting of aryl radicals and arylazo- I aryl radicals and n is a whole number included 7 R3N=N in the group consisting of land 2. 2. An azo dye having the following formula:

in which R3 and R4 are radicals included in the group consisting of aryl radicals and arylazo- N=N-R 0H aryl radicals and at least one of them is an aryl- 70 azoaryl radical.

MOSES L; CROSSLEY. BYRON L. WEST.

V 0 V in which R is an aromatic radical free from a groups. 

